A new approach for promoting ferric reduction efficiency using a different electrochemical cell and the photoelectro-Fenton process has been developed. The use of UVA light and electric current as electron donors can efficiently initiate the Fenton reaction. Benzene sulfonic acid (BSA) was the target compound in this study. The parameters investigated to evaluate the reactor design include the electrode working area, electrode distance, energy consumption. Furthermore, the study also contains the intermediates and the mineralization efficiency of electrolysis, Fenton, electro-Fenton and photoelectro-Fenton process. Oxalic acid, the major intermediate of aromatic compound degradation, can complex with ferric ions. Meanwhile, a double cathode reactor could increase the current efficiency by 7%, which would translate to greater ferrous production and a higher degradation rate. Although the current efficiency of an electrode distance 5.5 cm device is 19% higher than 3.0 cm, results show that after 2 h of electrolysis the electronic expense using an electrode gap of 5.5 cm is much higher than 3.0 cm. The final TOC removal efficiency was 46, 64 and 72% using the Fenton, electro-Fenton and photoelectron-Fenton processes, respectively.